EP0691355B1 - Cooligomère et copolymère à action dispersant - Google Patents

Cooligomère et copolymère à action dispersant Download PDF

Info

Publication number
EP0691355B1
EP0691355B1 EP95110071A EP95110071A EP0691355B1 EP 0691355 B1 EP0691355 B1 EP 0691355B1 EP 95110071 A EP95110071 A EP 95110071A EP 95110071 A EP95110071 A EP 95110071A EP 0691355 B1 EP0691355 B1 EP 0691355B1
Authority
EP
European Patent Office
Prior art keywords
copolymers
cooligomers
formula
meth
cnp
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95110071A
Other languages
German (de)
English (en)
Other versions
EP0691355A3 (fr
EP0691355A2 (fr
Inventor
Clemens Dr. Auschra
Horst Dr. Pennewiss
Susanne Graner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP0691355A2 publication Critical patent/EP0691355A2/fr
Publication of EP0691355A3 publication Critical patent/EP0691355A3/fr
Application granted granted Critical
Publication of EP0691355B1 publication Critical patent/EP0691355B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate

Definitions

  • the invention relates to dispersing cooligomers and Copolymers based on esters of (meth) acrylic acid alkoxylated alcohols with a certain content of Ethylene oxide or propylene oxide units, as emulsifiers especially for W / O emulsions, which are particularly suitable for the Application in the lubricating oil field (as so-called "Ashless Dispersants ”) are suitable.
  • cooligomers and copolymers CNP in which the radical R 2 in formula II is substituted by at least one group —NR 4 R 5 , where R 4 and R 5 independently of one another represent an alkyl radical having 1 to 20 carbon atoms or in which R 4 and R 5 , including the nitrogen atom and optionally a further oxygen or nitrogen atom, form a five- or six-membered ring which can be substituted by a C 1 -C 6 -alkyl radical.
  • examples include the dimethylamino group, the diethylamino group, the methyl-isopropylamino group, the piperidino group, the pyrrolidino group, the morpholino group and the like.
  • the molecular weights (M w ) of the cooligomers and copolymers are in the range from 1000 to 30,000 daltons, in particular in the range from 3,000 to 30,000 daltons (determination by gel permeation chromatography, see HF Mark et al. Encyclopedia of Polymer Science and Technology, Vol. 10 , 1-19, J. Wiley 1987; JV Dawkins Comprehensive Polymer Science, Vol. 1, 231 (1989), Pergamon Press).
  • Monomers of the formula I are in particular (meth) acrylic acid esters of mixtures of higher alcohols, in particular from the range from C 9 to C 20 , in particular from C 10 to C 18, with varying degrees of branching in the range from 25 to over 80%, for example those which come from the industrial scale Manufacturing processes such as oxo synthesis occur.
  • Examples include the esters of the so-called DOBANOL ® alcohols (products from Shell), the so-called ALFOL ® alcohols (products from Condea), the so-called LOROL ® alcohols, the tallow fatty alcohols and the like.
  • esters of alcohol mixtures from isomeric isodecyl alcohols esters of alcohol mixtures from isomeric isoundecyl alcohols and esters of an alcohol mixture with an average C number of 13.2-13.8 and a predominant content of C 12 -C 15 alcohols (DOBANOL ® 25L).
  • esters of cyclic alkanols for example having 5 to 8 ring carbon atoms, such as, for example, of cyclopentanol, cyclohexanol, cyclooctanol, benzyl alcohol, alkyl-substituted cyclohexanols, such as, for example, 4-tert-butylcyclohexanol, are also very useful.
  • Examples of compounds of the formula II are the (meth) acrylic esters of alkoxylated aliphatic alcohols, such as alkoxylated butanol and other alkoxylated alcohols, starting from: methanol, ethanol, propanol, pentanol (+ isomers), hexanol (+ isomers), cyclohexanol, methylcyclohexanol, 2-ethylhexanol and higher aliphatic monohydric alcohols such as isodecyl alcohol, isoundecyl alcohol, isotridecyl alcohol, fatty alcohols made from natural raw materials, etc.
  • alkoxylated aliphatic alcohols such as alkoxylated butanol and other alkoxylated alcohols, starting from: methanol, ethanol, propanol, pentanol (+ isomers), hexanol (+ isomers), cyclohexanol, methylcyclohexanol
  • alkoxylated phenols for example based on: phenol, alkyl-substituted phenols, for example t-butylphenol, 2,6-dimethylphenol, isomeric mixtures techn.
  • Alkylphenols for example octylphenol, nonylphenol, dinonylphenol, naphthol, alkyl-substituted naphthols, EO / PO addition products to substituted alcohols are also suitable, for example: furfurol, tetrahydrofurfurol, 2-methoxybutanol, 3-methoxybutanol, 2-dimethylaminoethaminoethanol, 2 -2-propanol, 3-dimethylamino-1-propanol, 2-morpholinoethanol, 2- (2-pyridyl) ethanol, N- (2-hydroxyethyl) piperidine, N- (2-hydroxyethyl) pyrrolidine, N- (2- Hydroxyethyl
  • Examples include alcohols, which represent a (statistical) adduct of ethylene oxide and propylene oxide with an alcohol such as butanol.
  • the molar ratio of the ethylene oxide and propylene oxide units in the monomer component B) can be between 96 to 4 and 6 to 94.
  • the range around 2,000 daltons is given. However, this is not a limitation.
  • higher molecular weights of up to approximately 5000 daltons can also be achieved.
  • the monomers of the formula II can themselves be present as a mixture consisting of methacrylates of the various alkoxylated alcohols described above.
  • the monomers of the formula III are the free-radically polymerizable 1-alkenes having 4 to 32 carbon atoms.
  • the C 4 -C 16 -alkenes for example 1-decene, 1-octene, 1-dodecene and 1-tetradecene, may be mentioned in particular , 1-hexadecene and also 1-octadecene, 1-eicosen.
  • the dispersion-effective oligomers (CNP-O) are prepared according to the rules and experience of radical polymerization (cf. CH Bamford, Encyclopedia of Polymer Science, Vol. 13, 708, 2nd. Ed. (1988)).
  • Known initiators come in particular organic radical initiators IN, preferably with a Decay temperature under normalized half-life conditions in the range 90 - 130 degrees C (see H. Logemann in Houben-Weyl, Methods of organ. Chemistry, 4th ed., Vol. XIV / I, S. 248, Georg Thieme (1961); Brandrup Immergut, polymer Handbook 3rd Ed., II-1, J. Wiley 1989) for example the group of organ.
  • Peroxy compounds especially with tertiary alkyl radicals, for example of 2,2-bis (tert-butyl-peroxy) butane, tert-butyl perbenzoate, di-tert-butyl peroxide, and Cumene hydroperoxide in question.
  • the initiators are used in amounts of approx. 0.01 up to 2 wt .-% based on the monomers used.
  • the Polymerization temperatures are generally relative high, for example above 120 degrees C and up to approx. 160 Degree C, advantageous at approx. 140 degrees C.
  • one suitable reactor for example one with a gas inlet, Stirring device, distillation attachment and thermometer equipped three-necked flask preferably under one Shielding gas such as nitrogen that is at the polymerization temperature - preheated to 140 degrees C, for example Solvent L submitted and the mixture of monomers over a period of time - for example during 3 Hours added continuously.
  • the template with the Monomer mixture is kept at 50 degrees C with stirring.
  • the initiator advantageously in one organic solvents (e.g. 50% in one aliphatic solvent) is added.
  • the addition process usually takes hours; about 8 hours are given as a guide. About 1/2 hour after the last addition, cool to a temperature in which the solvent L can be removed favorably, preferably for pressures in the millibar range, e.g. in the Oil pump vacuum.
  • the cooligomers and copolymers (CNP) according to the invention have an excellent emulsifier effect. They are suitable excellent for stabilizing water-in-oil emulsions (W / O emulsions). These properties can proven very well in the T / W (toluene / water) test, which specifically as a screening test for this effect was developed.
  • d-oligomer dispersing oligomers or Copolymers
  • ATF gear oil formulations
  • emulsifiers for W / O or O / W emulsions e.g. as emulsifiers for the Emulsion polymerization
  • stabilizers for Dispersions of inorganic and organic particles in Solvents e.g. in emulsion paints, as an aid for adhesives, e.g.
  • Monomer I-2 Methacrylic acid ester of an alcohol mixture of isomeric isodecyl alcohols
  • Alkene 1-decen Initiator solution
  • IN-1 2,2-bis (t-butylperoxy) butane 50% by weight dissolved in aliphatics (product INTEROX® BU-50-Al from Interox Corp.)
  • Solvent L Tetralin, decalin (mixture of isomers)
  • KV 100 Kinematic viscosity at 100 degrees C [mm 2 s -1 ] according to DIN 51 561
  • KV 40 Kinematic viscosity at 40 degrees C [mm 2 s -1 ] according to DIN 51 561
  • the additive to be tested for its emulsifying effect is described in Toluene (mixed with 20 ppm Oracet Blue B) with a Polymer concentration of 1 wt .-% dissolved.
  • Toluene mixed with 20 ppm Oracet Blue B
  • a Polymer concentration of 1 wt .-% dissolved In a graduated 20 ml test tubes are consecutively 7 ml dist. Water and 13 ml of the 1% toluene solution filled and 15 minutes in a water bath at 30 degrees C. tempered. By shaking the test tube vigorously a uniform emulsion is created and the sample in reset the temperature bath. The separation of the Emulsion into the layers Touol, emulsion and water observed over a period of 24 hours. To do this at the times 5 min, 10 min, 100 min and 24 hours Layer boundary toluene / emulsion and the layer boundary Read off the emulsion / water using the graduation (see Fig. 1a).
  • the quantification of the emulsifying effect in% values takes place according to the in Fig. 1b shown scheme.
  • the proportion of the emulsion present in the observation period of 5 minutes to 24 hours is characterized by the ratio of area A to total area A + B and is given in% values.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Claims (4)

  1. Cooligomères et copolymères à action dispersante à base d'esters d'acide (méth)acrylique comme agents émulsionnants,
    caractérisé en ce que
    les cooligomères et les copolymères (CNP) sont constitués de composants monomères qui renferment,
    A) de 60 à 95 % en poids d'au moins un ester d'acide (méth)acrylique de formule I
    Figure 00270001
    dans laquelle R représente de l'hydrogène ou un méthyle, et R1 représente un radial alkyle éventuellement ramifié ou un radical cycloalkyle ayant de 4 à 32 atomes de carbone dans le radical alkyle et,
    B) de 5 à 40 % en poids d'au moins un ester d'acide (méth)acrylique de formule II
    Figure 00270002
    dans laquelle R' représente de l'hydrogène ou un méthyle et R2 représente un radical alkyle ou aryle ayant de 1 à 50 atomes de carbone, dans laquelle R2 lui-même peut être substitué par de l'azote ou du soufre et dans laquelle n peut représenter une valeur numérique allant de 5 à 100 et m une valeur numérique allant de 0 à 100 et pour de 0 à 90 % molaire rapporté aux monomères de formule II un ester d'hydroxyalkyle d'acide (méth)acrylique de formule III,
    Figure 00280001
    dans laquelle R" représente de l'hydrogène ou un méthyle et R3 représente un radical alkyle substitué par au moins un groupe hydroxyle ayant de 2 à 30 atomes de carbone et avec la restriction que A) et B) se complètent à 100 % en poids.
    C) 0 - 75 parties en poids rapporté à la somme de A) et de B) d'au moins un 1-alkène ayant de 4 à 42 atomes de carbone dans la molécule dans laquelle les cooligomères et les copolymères (CNP) possèdent par détermination par chromatographie par perméation de gel des poids moléculaires (MW) allant de 1000 à 30.000 Daltons.
  2. Cooligomères et copolymères à action dispersante (CNP) conformément à la revendication 1,
    caractérisés en ce que
    le composant monomère B) est constitué d'unités d'oxyde d'éthylène et d'oxyde de propylène dans un rapport molaire allant de 96 pour 4 à 6 pour 94.
  3. Cooligomères et copolymères à action dispersante (CNP) conformément à la revendication 2,
    caractérisés en ce que
    les unités d'oxyde d'éthylène et les unités d'oxyde de propylène sont distribuées statistiquement.
  4. Cooligomères et copolymères à action dispersante (CNP) conformément aux revendications 1 à 3,
    caractérisés en ce que
    le radical R2 des monomères de formule II est substitué par au moins un groupe NR4R5 dans lequel R4 et R5, indépendamment l'un de l'autre, représentent un radical alkyle ayant de 1 à 20 atomes de carbone ou dans lequel R4 et R5 impliquant l'atome d'azote et le cas échéant un autre atome d'oxygène ou d'azote, forment un cycle à cinq ou six maillons qui peut être substitué par un radical alkyle ayant de 1 à 6 atomes de carbone.
EP95110071A 1994-07-04 1995-06-28 Cooligomère et copolymère à action dispersant Expired - Lifetime EP0691355B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4423358 1994-07-04
DE4423358A DE4423358A1 (de) 1994-07-04 1994-07-04 Dispergierwirksame Cooligomere und Copolymere

Publications (3)

Publication Number Publication Date
EP0691355A2 EP0691355A2 (fr) 1996-01-10
EP0691355A3 EP0691355A3 (fr) 1996-04-10
EP0691355B1 true EP0691355B1 (fr) 1999-04-21

Family

ID=6522183

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95110071A Expired - Lifetime EP0691355B1 (fr) 1994-07-04 1995-06-28 Cooligomère et copolymère à action dispersant

Country Status (5)

Country Link
US (1) US5712359A (fr)
EP (1) EP0691355B1 (fr)
JP (1) JP3698759B2 (fr)
AT (1) ATE179188T1 (fr)
DE (2) DE4423358A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010118924A1 (fr) 2009-04-15 2010-10-21 Evonik Röhm Gmbh Procédé de production d'homo- et de copolymères contenant un (méth) acrylate d'(alcoxy) polyalkylèneglycol, et utilisation des polymères ainsi produits

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69227043T2 (de) * 1992-01-31 1999-02-18 Du Pont Verfahren zur herstellung von lichtempfindlichem elastomeren mit verbessertem belichtungsspielraum
DE19603696A1 (de) * 1996-02-02 1997-08-07 Roehm Gmbh Demulgatoren
US7008992B1 (en) 1998-07-22 2006-03-07 E. I. Du Pont De Nemours And Company Water insoluble non-ionic graft copolymers
EP1069142B1 (fr) * 1999-07-15 2010-04-28 Clariant Produkte (Deutschland) GmbH Polymères solubles dans l'eau et leur utilisation dans des produits cosmétiques et pharmaceutiques
US6214958B1 (en) * 1999-07-21 2001-04-10 Arco Chemical Technology, L.P. Process for preparing comb-branched polymers
DE19958447A1 (de) * 1999-12-03 2001-06-07 Basf Ag Verfahren zur Herstellung von wasserlöslichen Polymerisaten, die Polyalkylenglykolether-Seitenketten enthalten
DE10055470A1 (de) * 2000-11-09 2002-05-29 Fraunhofer Ges Forschung Verfahren zur Polymerisation wasserlöslicher Vinylmonomerer in wäßrigen höherkonzentrierten Dispersionen und Stabilisator zur Durchführung des Verfahrens
DE10059819A1 (de) * 2000-12-01 2002-06-13 Clariant Gmbh Tensidhaltige kosmetische, dermatologische und pharmazeutische Mittel
DE10059821A1 (de) * 2000-12-01 2002-06-13 Clariant Gmbh Tensidfreie kosmetische, dermatologische und pharmazeutische Mittel
US6951642B2 (en) 2001-09-28 2005-10-04 3M Innovative Properties Company Water-in-oil emulsions with anionic groups, compositions, and methods
US7030203B2 (en) 2001-09-28 2006-04-18 3M Innovative Properties Company Water-in-oil emulsions with ethylene oxide groups, compositions, and methods
FR2901928B1 (fr) * 2006-05-31 2008-09-05 Valeo Equip Electr Moteur Procede et dispositif de generation de signaux de commande d'une machine electrique tournante polyphasee en fonction de la vitesse
DE102009019177A1 (de) * 2009-04-28 2010-11-11 Clariant International Ltd. Verwendung biologisch abbaubarer alkoxylierter (Meth)acrylat-Copolymere als Rohöl-Emulsionsspalter
DE102010001040A1 (de) 2010-01-20 2011-07-21 Evonik RohMax Additives GmbH, 64293 (Meth)acrylat-Polymere zur Verbesserung des Viskositätsindexes
FR2956862B1 (fr) * 2010-02-26 2013-03-15 Coatex Sas Monomere associatif a base d'alcools oxo, polymere acrylique contenant ce monomere, utilisation dudit polymere comme epaississant dans une formulation aqueuse, formulation obtenue.
CN102660338B (zh) * 2012-04-26 2014-02-12 安徽大学 一种用于提高生物柴油低温流动性的改进剂及其制备方法
US20180298306A1 (en) * 2017-04-06 2018-10-18 Wd-40 Company Non-flammable aerosol multiuse invert emulsion lubricant

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL238305A (fr) * 1958-04-21
DE1745359B2 (de) 1964-06-06 1976-06-10 Röhm GmbH, 6100 Darmstadt Verfahren zur herstellung von schmieroelzusaetzen
US3651029A (en) * 1968-08-26 1972-03-21 Sanyo Chemical Ind Ltd Lubricating oil additives
JPS5937826B2 (ja) * 1977-09-08 1984-09-12 三洋化成工業株式会社 電子写真用液体現像剤の顔料分散剤
DE2805826A1 (de) 1978-02-11 1979-08-23 Roehm Gmbh Verbesserte pfropfverfahren
DE2905954C2 (de) 1979-02-16 1982-10-28 Röhm GmbH, 6100 Darmstadt Konzentrierte Polymerisatemulsionen als Viskositätsindexverbesserer für Mineralöle
DE3207292A1 (de) 1982-03-01 1983-09-08 Röhm GmbH, 6100 Darmstadt Konzentrierte emulsionen von olefincopolymerisaten
DE3207291A1 (de) 1982-03-01 1983-09-08 Röhm GmbH, 6100 Darmstadt Konzentrierte emulsionen von olefincopolymerisaten
DE3930142A1 (de) 1989-09-09 1991-03-21 Roehm Gmbh Dispergierwirksame viskositaets-index-verbesserer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010118924A1 (fr) 2009-04-15 2010-10-21 Evonik Röhm Gmbh Procédé de production d'homo- et de copolymères contenant un (méth) acrylate d'(alcoxy) polyalkylèneglycol, et utilisation des polymères ainsi produits
DE102009002401A1 (de) 2009-04-15 2010-10-21 Evonik Röhm Gmbh Verfahren zur Herstellung von (Alkoxy)polyalkylenglycol(meth)acrylat enthaltendem Homo- und Copolymeren sowie die Verwendung derartig ergestellter Polymerisate

Also Published As

Publication number Publication date
DE59505684D1 (de) 1999-05-27
JP3698759B2 (ja) 2005-09-21
JPH0848727A (ja) 1996-02-20
US5712359A (en) 1998-01-27
DE4423358A1 (de) 1996-01-11
EP0691355A3 (fr) 1996-04-10
ATE179188T1 (de) 1999-05-15
EP0691355A2 (fr) 1996-01-10

Similar Documents

Publication Publication Date Title
EP0691355B1 (fr) Cooligomère et copolymère à action dispersant
EP0699694A2 (fr) Polymères en peigne
EP0621293B1 (fr) Polymères à structure en peigne
EP0880572B1 (fr) Utilisation des demulsifiants
EP3099768B1 (fr) Inhibiteurs de corrosion pour carburants
DE60015606T2 (de) Zusammensetzungen, enthaltend aminische antioxidantien auf basis von n-(4-anilinophenyl)amiden
EP0014746B1 (fr) Additifs pour huile lubrifiante
EP2526135B1 (fr) Polymère de méth(acrylate) pour l'amélioration de l'indice de viscosité
DE19518786A1 (de) Schmierstoffadditive
EP2197965B1 (fr) Liant aqueux pour substrats fibreux ou granuleux
DE102004044879A1 (de) Copolymerisate, deren Herstellung und Verwendung als Netz- und Dispergiermittel
EP0522376B1 (fr) Procédé de préparation de macromonomères de polyméthacrylate d'alcoyle
DE2422609A1 (de) Schmieroelformulierung
EP2152801B1 (fr) Dispersions polymères améliorées
WO2000050543A1 (fr) Polyalcoxylates de polyalcenealcool et leur utilisation dans des carburants et des lubrifiants
DE4021095A1 (de) Viskositaetsindex-verbesserer und verfahren zu seiner herstellung
DE4025493A1 (de) Verfahren zur herstellung von homooligomeren und cooligomeren
DE19506399A1 (de) Pfropfpolymere mit Emulgatoreigenschaften
DE102005025739A1 (de) Copolymerisierbare Polyalkylenglykol-Makromonomere, deren Herstellung und Verwendung
EP0773260A2 (fr) Emulsions de polymères à distributions de poids moléculaires bimodales
DE2810248A1 (de) Oelloesliches produkt und seine verwendung
DE60009687T3 (de) Verfahren zur herstellung von durch freiem radikal polymerisierte polymere
DE19847423A1 (de) Additiv für Biodiesel und Biobrennstofföle
US3278500A (en) Sulfur-containing polymers
EP1177270A1 (fr) Polyalcene-alcool-polyetheramines et leur utilisation dans les carburants et les lubrifiants

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19960914

17Q First examination report despatched

Effective date: 19970122

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19990421

REF Corresponds to:

Ref document number: 179188

Country of ref document: AT

Date of ref document: 19990515

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59505684

Country of ref document: DE

Date of ref document: 19990527

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990721

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19990723

BERE Be: lapsed

Owner name: ROHM G.M.B.H.

Effective date: 19990630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: ROEHM GMBH & CO. KG

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: FR

Ref legal event code: CJ

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20080625

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20080612

Year of fee payment: 14

Ref country code: NL

Payment date: 20080618

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080613

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080620

Year of fee payment: 14

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090628

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20100101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090629

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20110622

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59505684

Country of ref document: DE

Effective date: 20130101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130101